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WO1992007030A1 - Phosphites de tris-(2-alkyle-4-alcoxyphenyle) utilises en tant que stabilisateurs de traitement pour des polyolefines - Google Patents

Phosphites de tris-(2-alkyle-4-alcoxyphenyle) utilises en tant que stabilisateurs de traitement pour des polyolefines Download PDF

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Publication number
WO1992007030A1
WO1992007030A1 PCT/US1991/007198 US9107198W WO9207030A1 WO 1992007030 A1 WO1992007030 A1 WO 1992007030A1 US 9107198 W US9107198 W US 9107198W WO 9207030 A1 WO9207030 A1 WO 9207030A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
polyolefins
tris
compound
phosphites
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1991/007198
Other languages
English (en)
Inventor
Richard Hsu-Shien Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1019920701373A priority Critical patent/KR927003708A/ko
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of WO1992007030A1 publication Critical patent/WO1992007030A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • This invention concerns pertains to the use of certain tris—(2—alkyl—4—alkoxyphenyl) phosphites as processing stabilizers for polyolefins.
  • This invention also pertains to a method of inhibiting thermally- induced, oxidative degradation of polyolefins by the addition thereto of at least one of the tris-phosphite compounds.
  • Synthetic polymeric materials such as polyolefins, particularly polypropylene, require stabilization against thermal degradation to prevent significant changes in the properties of the polymeric material during melt processing.
  • a stabilizer normally is added to polyolefins shortly after they are manufactured.
  • the melt—flow rate of polypropylene changes significantly during its extrusion in the compounding of various formulations and products.
  • Various cyclic phosphites (and the use thereof in polyolefins) are well— nown. See, for example, U.S. Patents 3,441,633, 3,467,733, 3,592,858 and 3,714,302 and French Patent 1,501,427.
  • phosphites possess moderate to poor storage stability which imparts poor handling properties and causes their effectiveness as polyolefin stabilizers to diminish when they are stored over a period of time, especially in areas of high humidity.
  • the phosphites employed in accordance with the present invention exhibit excellent storage stability and are effective process stabilizers for polyolefins.
  • compositions of the present invention comprise a poly— ⁇ -olefin susceptible to degradation upon exposure to heat and/or radiation containing a stabilizing amount of a compound having the formula
  • R 1 is hydrogen, alkyl or aralkyl
  • R 2 is hydrogen or alkyl
  • R 3 is alkyl or aryl.
  • alkyl groups represented by R 1 , R 2 and R 3 include alkyl containing up to 8 carbon such as methyl, ethyl, propyl, 2—propyl, butyl, 2—butyl, 2—methyl—2— propyl, pentyl, 2—pentyl, hexyl, 2—ethyl—hexyl, 2,4,4—trimethyl—2—pentyl.
  • the alkyl groups represented by R 1 , R 2 and R 3 preferably contain up to 4 carbon atoms.
  • the aryl group represented by R 3 and the aryl moiety of the aralkyl radical represented by R 1 may be unsubstituted phenyl or phenyl substituted with 1 or 2 groups selected from lower, i.e., containing up to 4 carbon atoms, alkyl, lower alkoxy or halogen, e.g., chlorine or bromine.
  • the alkyl moiety of the aralkyl groups typically is lower alkyl.
  • the aryl group representec* by R 3 and the aryl moiety of the aralkyl radical represented by R 1 preferably are unsubstituted phenyl.
  • the compounds of formula (I) may be prepared by reacting phosphorus trichloride with an alkylated hydroquinone or mono—alkyl ether of an alkylated hydroquinone compound having the formula according to known procedures, wherein R 1 , R 2 and R 3 are defined above.
  • Examples of the compounds of formula (II) are 2-(l,l-dimethylethyl)—4—methoxyphenol,
  • the stabilized composition of my invention preferably contain a stabilizing amount of a phosphite compound having the formula
  • R 2 and R 3 each is methyl or ethyl.
  • EXAMPLE 1 Phosphorus trichloride (22.9 g, 0.167 mole) is added dropwise over a period of 20 minutes to a solution of 2—(1,1-dimethylethyl)—4—methoxyphenol (90 g, 0.5 mole), pyridine (0.5 g) and xylene (17 g) at 50°C.
  • the reaction mixture is heated at 50 ⁇ C for 1 hour and then is heated to and held at 130 ⁇ for 2 hours. After distilling off some low boiling material under reduced pressure, the reaction mixture is cooled to 90°C, 200 mL 2-propanol are added and the resulting mixture is cooled 15°C.
  • the product is collected by filtration, washed with cold 2-propanol and dried.
  • the product, tris-[2- (l,l-dimethylethyl)-4-methoxyphenyl] phosphite is obtained in a yield of 58% and has a melting temperature of 82-86°C.
  • the tris-phosphite compounds of formula (I) may be used in a wide variety of polyolefin materials which are susceptible to degradation upon exposure to heat and/or radiation including both visible and ultraviolet light.
  • polyolefin materials which are susceptible to degradation upon exposure to heat and/or radiation including both visible and ultraviolet light.
  • examples of such materials include homo— and co—polymers of ⁇ —olefins such as polyethylene, polypropylene, polybutene, poly—3— ethylbutene and ethylene—propylene copolymers and ethylene—vinyl acetate copolymers.
  • the preferred stabilized compositions of my invention comprise homo— and co—polymers of a—olefins of 2 to 4 carbon atoms, especially polypropylene, containing a stabilizing amount of one or more of the compounds of formula (I) .
  • concentration of the phosphite compound in the polymeric material which will effectively inhibit polymer degradation can vary considerably depending on the particular polymer being stabilized and the end use for which the stabilized polymeric material is designed. Generally, concentration in the range of 0.001 to 5.0 weight percent may be used with concentrations of 0.01 to 0.5 being most common.
  • the phosphite stabilizer may be incorporated into the polymeric materials by conventional blending techniques.
  • the stabilizer may be added directly to a melt of the polymer on a roll mill to distribute the phosphite compound uniformly throughout the polymer.
  • the phosphite compound may be dry—blended with a finely-divided form of the polymer such as pellets and then the dry mix can be mixed further in and extruded from an extruder.
  • Phosphites function as processing stabilizers in polyolefins by decomposing hydroperoxides which initiate the thermal degradation of polyolefins.
  • hydroperoxide decomposing capability is reduced drastically.
  • the control sample contained no phosphite compound.
  • Each polypropylene sample was extruded five times. After each extrusion, the melt- flow rate (ASTM Method D 1238, Procedure A, Condition E; g/10 minutes) is determined for each sample.
  • the inhibiting effect of each phosphite compound on the thermal degradation of the polypropylene is shown in Table II wherein the melt flow rates of the polypropylene samples prepared and extruded as described above are set forth.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions de polyoléfines renfermant un composé de phosphite de la formule (I) dans laquelle R1 représente hydrogène, alkyle ou aralkyle; R2 représente hydrogène ou alkyle; et R3 représente alkyle ou aryle.
PCT/US1991/007198 1990-10-10 1991-10-08 Phosphites de tris-(2-alkyle-4-alcoxyphenyle) utilises en tant que stabilisateurs de traitement pour des polyolefines Ceased WO1992007030A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019920701373A KR927003708A (ko) 1990-10-10 1990-10-08 폴리올레핀에 사용하기 위한 가공 안정화제로서 트리스-(2-알킬-4-알콕시페닐)포스파이트

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/596,655 US5112893A (en) 1990-10-10 1990-10-10 Tris-(2-alkyl-4-alkoxyphenyl) phosphites as processing stabilizers for polyolefins
US596,655 1990-10-10

Publications (1)

Publication Number Publication Date
WO1992007030A1 true WO1992007030A1 (fr) 1992-04-30

Family

ID=24388157

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/007198 Ceased WO1992007030A1 (fr) 1990-10-10 1991-10-08 Phosphites de tris-(2-alkyle-4-alcoxyphenyle) utilises en tant que stabilisateurs de traitement pour des polyolefines

Country Status (6)

Country Link
US (1) US5112893A (fr)
EP (1) EP0504379A1 (fr)
JP (1) JPH05502693A (fr)
KR (1) KR927003708A (fr)
CA (1) CA2070292A1 (fr)
WO (1) WO1992007030A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412064A (en) * 1965-11-08 1968-11-19 Uniroyal Inc Olefin polymer composition
US3467737A (en) * 1965-11-08 1969-09-16 Uniroyal Inc Phenolic phosphites
EP0032202A1 (fr) * 1979-12-17 1981-07-22 Bayer Ag Procédé pour la préparation d'esters aryliques neutres de l'acide phosphoreux

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE622653A (fr) * 1961-09-21
US3558554A (en) * 1966-06-09 1971-01-26 Yoshitomi Pharmaceutical Oxidatively stable polyolefin composition
US3567683A (en) * 1968-09-08 1971-03-02 Goodyear Tire & Rubber Composition of matter
JPS5512174A (en) * 1978-07-13 1980-01-28 Adeka Argus Chem Co Ltd Stabilized halogen-containing resin composition
US4384062A (en) * 1980-10-01 1983-05-17 Uniroyal, Inc. Hydrolytically stable diphosphites useful as antioxidants
JPS5927936A (ja) * 1982-08-09 1984-02-14 Sumitomo Chem Co Ltd 安定化ポリオレフイン樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412064A (en) * 1965-11-08 1968-11-19 Uniroyal Inc Olefin polymer composition
US3467737A (en) * 1965-11-08 1969-09-16 Uniroyal Inc Phenolic phosphites
EP0032202A1 (fr) * 1979-12-17 1981-07-22 Bayer Ag Procédé pour la préparation d'esters aryliques neutres de l'acide phosphoreux

Also Published As

Publication number Publication date
EP0504379A1 (fr) 1992-09-23
JPH05502693A (ja) 1993-05-13
US5112893A (en) 1992-05-12
CA2070292A1 (fr) 1992-04-11
KR927003708A (ko) 1992-12-18

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